Method of adhesion of rubber to reinforcing materials

ABSTRACT

A vulcanizable rubber composition comprising a rubber, a vulcanizing agent and glyoxal or a glyoxal reaction product and a method of adhering fiber or steel tire cord, are disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of copending application Ser. No. 8204, filed Jan. 31, 1979, now U.S. Pat. No. 4,228,045, and entitled METHOD OF ADHESION OF RUBBER TO REINFORCING MATERIALS AND COMPOSITION THEREFOR

BACKGROUND OF THE INVENTION

It has been conventional practice to prepare various textile reinforcing fibers, to be used in contact with rubber compositions, by pretreating them with a rubber latex and a phenol-formaldehyde resin, in which the phenol has almost always been resorcinol. This is the so-called "RFL" (Resorcinol-Formaldehyde-Latex) method. Another method commonly used is to generate the resin in situ in the vulcanized rubber-textile matrix by incorporating therein a formaldehyde (or methylene) donor compound, e.g., hexamethylenetetramine or hexamethoxymethylmelamine, and a formaldehyde (or methylene) acceptor compound, e.g., resorcinol. This method has been particularly effective where the reinforcing material is brass-coated steel wire, since pretreatment of the wire by the aforementioned "RFL" method has proven to be largely ineffective. The methylene donor-acceptor method is described by Endter, U.S. Pat. No. 3,517,722.

SUMMARY OF THE INVENTION

It has been found that excellent adhesion of rubber to reinforcing materials, such as textile fibers and steel wire, is achieved by the incorporation into the rubber composition, before vulcanization thereof in the presence of reinforcing materials, of (a) glyoxal, (b) a reaction product of glyoxal and urea, or (c) a reaction product of glyoxal, urea, and formaldehyde, as defined hereinbelow.

Such materials have not been used heretofore in adhesion of textile fibers or steel wire to rubber. Moreover, it is quite surprising that excellent adhesion, equal to or better than that which is obtained by present methods, is achieved by the use of glyoxal alone, since it would seem to deviate from the commonly accepted methylene donor-acceptor theory of adhesion. The method of the present invention has the advantage of achieving adhesion with a one-component, readily obtained promoter system.

DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS

As used herein, the term "glyoxal" means commercially available forms of glyoxal including anhydrous, monomeric glyoxal which is described as a low melting (15° C.), low boiling (51° C.) compound. "Glyoxal", also includes aqueous solutions of glyoxal with or without small concentrations of formaldehyde, in that most commercially available glyoxal solutions will contain from about 0.01 to about 0.4 moles of formaldehyde per mole of glyoxal. It is known that when aqueous solutions of glyoxal, of concentrations greater than about 40 percent, are allowed to stand for prolonged periods of time, the hydrated trimer (I) separates as a crystalline product. ##STR1##

Simple vacuum distillation or stripping below 100° C. produces a hydrated polymer containing as little as 5 percent water, which corresponds to the polymer of formula (II) wherein n=12 and m=2. ##STR2##

"Glyoxal" may also be considered to be 1,1,2,2-tetrahydroxyethane (III) in equilibrium with smaller amounts of glyoxal dimer (IV) and the trimer (I), as follows: ##STR3##

Thus, in accordance with the present invention, any one or more or all of the forms described above alone or in admixture, as well as glyoxal monomer (V), which structure is oftimes set forth in the prior art as representative of glyoxal, ##STR4## can be used herein.

Reaction products of glyoxal and urea are readily obtained by the condensation of 0.1 to 10, preferably 0.5 to 4, molar proportions, or more, of urea with one molar proportion of glyoxal. The reaction products are ordinarily resinous mixtures. A desirable, and preferred species, of urea/glyoxal reaction product, which may be isolated as a crystalline compound from the reaction mixtures in the presence of water is 4,5-dihydroxyethylene urea (VI), commonly designated DHEU, ##STR5## (Note: The proper chemical name is 4,5-dihydroxy-2-imidazolidinone. A method for its preparation is taught in U.S. Pat. No. 3,260,565).

Even more preferred species of glyoxal/urea reaction products are those obtained by reacting glyoxal and urea at mole ratios of 1/1-1/1.5 (from which DHEU may be isolated in the presence of water, as shown in the accompanying examples).

Reaction products of glyoxal, 1-2 moles of urea, and 1-2 moles of formaldehyde are also useful adhesion promoters in accordance with this invention. Preferred species are 1-methylol- and 1,3-dimethylol-4,5-dihydroxy--2-imidazolidinone (VII) and (VIII), respectively, which can be prepared by reacting about 1 mole of DHEU with 1-2 moles of formaldehyde, when the DHEU is recovered as such. Products VII and VIII are also formed, in situ, when the glyoxal, urea and formaldehyde are charged together, as described above. ##STR6##

As can be readily appreciated, when a commercially available glyoxal solution which contains formaldehyde as mentioned above is employed as the glyoxal charge with which the urea is reacted, the resultant products will contain small amounts of compounds (VII) and (VIII) as well as urea-glyoxal-formaldehyde resinous mixtures.

It is pointed out, however, that the presence of formaldehyde has a deleterious effect on the physical properties of the vulcanized rubber, although adhesion properties are good. Thus, although reaction products of glyoxal and urea, as described hereinabove, may contain as much as 10 moles of urea per mole of glyoxal, it is disadvantageous to react more than 2 molar proportions of formaldehyde therewith, since the physical properties of the vulcanized rubber to which such products are added are negatively affected thereby. Moreover, optimum adhesion results, with minimum loss in rubber properties, are obtained when glyoxal containing less than about 0.4 moles of formaldehyde, is used.

The improved adhesion promoters of the present invention may be used in bonding reinforcing fibers or wire to rubber used in the manufacture of tires, drive belts, conveyor belts, pressure hoses, and the like. The rubber used may be natural rubber; synthetic diene rubbers, such as polybutadiene, polyisoprene; ethylene-propylene terpolymer rubbers (EPDM); butadiene-styrene copolymer rubbers (SBR); butadiene-acrylonitrile copolymer rubbers (NBR); chloroprene rubber; chlorosulfonated polyethylene; or mixtures thereof.

The reinforcing materials useful herein include textile materials, in the form of fibers or fabric, commonly used to reinforce rubber compositions, which include cotton, rayon, polyamides, polyesters, polyimides, and the like, and metal materials such as wires and cord threads of raw steel, zinc-coated steel and the like. A particularly useful reinforcing material found to form strong adhesive bonds with rubber in accordance with this invention is brass-coated steel wire.

The vulcanizable rubber composition to which the reinforcing materials are bonded during vulcanization contain, in addition to the promoter compound of the invention, other conventional compounding ingredients such as carbon black, antioxidants, sulfur, zinc oxide, accelerators, high surface area silica (including mixtures thereof with carbon black), processing and softening oils, and the like.

The glyoxal or glyoxal reaction product is incorporated into the vulcanizable composition in an amount of from about 1 to 10 parts, by weight, per one hundred parts of weight of rubber used. Preferably, the compounds are used in an amount of from about 2 to 4 parts, by weight, same basis.

For optimum adhesion of the reinforcing material to rubber, particularly when using a metal such as brass-coated steel wire, it has been found desirable to incorporate a high surface area silica into the vulcanizable rubber composition. The reason for enhanced adhesion in the presence of a high surface area silica is speculative, but may result from hydrogen bonding of hydroxyl groups of the silica with the components of the vulcanizable system. The silica is used in an amount of from about 2 to 14 parts, by weight, per hundred parts of rubber, preferably about 8 to 12 parts per hundred of rubber although good adhesion is still achieved in the absence of the silica.

The use of glyoxal, or one of the glyoxal-urea reaction products, is facilitated by first absorbing the liquid onto an inert solid carrier, such as the aforementioned high surface area silica; precipitated, hydrous calcium silicate, and the like, and adding the compound to the rubber as a free-flowing solid.

Adhesion is measured using ASTM D-2229-73 with 15 reinforcing members embedded in a 0.5"×0.5"×8" block of rubber. The force to pull the metal wire or textile fiber out of the rubber is recorded in pounds per linear inch (pli) of embedded length, except that in the table following Example 29, a modification was employed whereby seven alternating reinforcing members are pulled while holding the specimen by the two adjacent wires protruding from the opposite side of the sample (the "Harp" test). This modification has little effect on the recorded adhesion values.

The following examples are provided to illustrate the particular features of the invention. Unless otherwise specified, all parts are by weight.

EXAMPLE A Preparation of 4,5-Dihydroxyethyleneurea

A 40% glyoxal solution, formaldehyde free, (321 parts; 2.2 moles), is diluted with 107 parts of water to give a 30% solution, and adjusted to pH 7 with 5 N NaOH. While stirring at room temperature, 200 parts (3.34 moles) of prilled urea is added and the mixture stirred at 25°-30° C. for about 2 hours. The reaction mixture is poured into an open tray, and after 2 to 3 hours, crystals form which are filtered, stirred with 160 parts of methanol and filtered again. The crystals are recrystallized from 500 parts of 40% aqueous methanol. There is obtained a yield of 75.5 parts, m.p. 152° C. (dec.) of 4,5-dihydroxyethyleneurea.

EXAMPLE B Preparation of Glyoxal-Urea Reaction Product (molar ratio 1.0:0.5)

Urea (30 parts, 0.5 mole) and glyoxal (145.1 parts of 40% aqueous solution, formaldehyde free, 1.0 mole), adjusted to pH 7 with 5 N soldium hydroxide, are reacted for about 3 hours at 25°-30° C. The reaction mixture, containing 50.3% solids, is poured into an open tray and permitted to stand open to the atmosphere to evaporate water therefrom. After several hours standing, a composition is obtained containing 78% solids.

EXAMPLES C-K

Following the general procedure of Example 3, glyoxal-urea reaction products are prepared as shown in the following table:

    ______________________________________                                         Example     Glyoxal/Urea (moles)                                                                             % Solids                                         ______________________________________                                         C           1.0/1.0           74.4                                             D           1.0/1.5           74.4                                             E           1.0/2.0           77.7                                             F           1.0/2.5           88.7                                             G           1.0/3.0           89.3                                             H           1.0/3.5           88.6                                             I           1.0/4.0           84.2                                             J           1.0/6.0           60.0                                             K            1.0/10.0         60.0                                             ______________________________________                                    

EXAMPLE L Preparation of Glyoxal-Urea Reaction Product on Hydrous Calcium Silicate (mole ratio 1:0.5)

Urea (60 parts, 1.0 mole) and glyoxal (290 parts of 40% solution containing 5% formaldehyde; 116 parts, 2.0 moles), adjusted to pH 7 with 5 N sodium hydroxide, are reacted for 3 hours at 25°-30° C. The reaction product (140 parts) is absorbed onto 60 parts of precipitated hydrous calcium silicate and the mixture is dried at 70° C. for about 16 hours. The product is passed through a 60 mesh screen. Active urea-glyoxal reaction product is 50 percent.

EXAMPLES M-U

Following the general procedure of Example L, glyoxal-urea-formaldehyde reaction products are prepared as shown in the following table:

    ______________________________________                                         Example     Glyoxal/Urea (moles)                                                                             % Active                                         ______________________________________                                         M           1.0/1.0           57.5                                             N           1.0/1.5           62                                               O           1.0/2.0           63.2                                             P           1.0/2.5           65.5                                             Q           1.0/3.0           67.9                                             R           1.0/3.5           65.3                                             S           1.0/4.0           65.6                                             T           1.0/6.0           60                                               U            1.0/10.0         60                                               ______________________________________                                    

EXAMPLE V Preparation of 1-Methylol-4,5-Dihydroxy-2-Imidazolidinone ##STR7##

Formaldehyde (8.85 parts of 37.3 percent solution; 0.11 mole), adjusted to pH 7-8.5, is diluted with water (20 parts). While stirring, 11.8 parts (0.1 mole) of dihydroxyethyleneurea powder are added. The temperature is raised to 55° C., held at 55° C. for 30 minutes, cooled to room temperature, and refrigerated. The sample is recovered as an 80 percent aqueous solution.

EXAMPLE W Preparation of 1,3-Dimethylol-4,5-Dihydroxy-2-Imidazolidinone ##STR8##

An aqueous solution containing 45 percent by weight of the subject compound, prepared according to the procedure of Chao, U.S. Pat. No. 3,903,033, Example 1, is evaporated to give a solution containing 90 percent by weight of the compound.

A polyblend of natural rubber polybutadiene and a styrene-butadiene (25/75) rubber is compounded as follows and used in the evaluation of the adhesion promoters of the invention:

    ______________________________________                                         Polyblend Masterbatch Formulation                                              ______________________________________                                         Natural rubber             52                                                  Polybutadiene              18                                                  Styrene-butadiene rubber   30                                                  Carbon black               40                                                  Zinc oxide                  5                                                  Stearic acid                2                                                  Reaction product of diphenylamine                                                                          2                                                  and acetone; 50 percent active                                                 Silica (high surface area) 10                                                  ______________________________________                                    

Similarly, a natural rubber masterbatch is compounded as follows:

    ______________________________________                                         Natural Rubber Masterbatch Formulation                                         ______________________________________                                         Natural rubber             100                                                 Carbon black               40                                                  Zinc oxide                 5                                                   Stearic acid               2                                                   Reaction product of diphenylamine                                                                         2                                                   and acetone; 50 percent active                                                 Silica (high surface area) 10                                                  ______________________________________                                    

In the following example, one or the other of the polyblend or natural rubber masterbatch formulations is used, in each case in an amount containing 100 parts of rubber.

EXAMPLES 1-3

Dihydroxyethyleneurea (DHEU) is evaluated as an adhesion promoter in natural rubber as follows:

    ______________________________________                                         Compositions   Control A 1       2     3                                       ______________________________________                                         Natural rubber 158.5     158.5   158.5 158.5                                   masterbatch                                                                    Sulfur         3.75      3.75    3.75  3.75                                    N-oxydiethylene benzo-                                                                        0.8       0.8     0.8   0.8                                     thiazole-2-sulfenamide                                                         Dihydroxyethyleneurea                                                                         --        1       2     3                                       ______________________________________                                    

The compositions are compounded on a standard rubber mill for 10 minutes at 120° to 175° F., embedded with 15 clean, brass-coated steel wires, placed parallel, and vulcanized at 307° F. Properties are given below:

    ______________________________________                                         Stress-Strain and                                                                             Control                                                         Adhesion Properties                                                                           A         1       2     3                                       ______________________________________                                         Modulus @ 300%, psi                                                                           1662      1624    1660  1790                                    Tensile, psi   3883      3965    3676  3583                                    Elongation, %   541       543     546   501                                    Adhesion, pli   127       160     182   225                                    ______________________________________                                    

The data illustrate that dihydroxyethyleneurea improves the adhesion of steel wire to rubber.

EXAMPLES 4-12

Glyoxal liquid (containing no formaldehyde; 67.5% aqueous solution) and various urea-glyoxal reaction products made therefrom as shown in Examples B-I, are evaluated as adhesion promoters in natural rubber as follows:

    __________________________________________________________________________     Compositions                                                                            Control B                                                                            Comparative                                                                           4 5 6 7 8 9 10                                                                               11                                                                               12                                       __________________________________________________________________________     Natural rubber                                                                          158.5                                                                 masterbatch                                                                    Sulfur   3.75                                                                  N-oxydiethylene                                                                         0.8                                                                   benzothiazole-2-                                                               sulfenamide                                                                    Urea           3                                                               Glyoxal liq.          3                                                        (67.5%)                                                                        Urea-Glyoxal                                                                   Products                                                                       0.5/1                   3                                                      1.0/1                     3                                                    1.5/1                       3                                                  2.0/1                         3                                                2.5/1                           3                                              3.0/1                             3                                            3.5/1                               3                                          4.0/1                                 3                                        __________________________________________________________________________

The compositions are compounded on a standard rubber mill for 10 minutes at 120° to 175° F., embedded with 15 clean, brass-coated steel wires, placed parallel, and vulcanized at 307° F. Properties are given below.

    __________________________________________________________________________     Stress-Strain                                                                  and Adhesion Properties                                                                    Control                                                                             Comparative                                                                           4  5  6  7  8  9  10 11 12                             __________________________________________________________________________     Modules % 300%, psi                                                                        1848 2246   1677                                                                              1868                                                                              1718                                                                              1905                                                                              2103                                                                              1991                                                                              2044                                                                              2138                                                                              2059                           Tensile, psi                                                                               3939 3143   3796                                                                              3858                                                                              3948                                                                              3858                                                                              3583                                                                              3541                                                                              3446                                                                              3612                                                                              3382                           Elongation, %                                                                               529  392    541                                                                               536                                                                               560                                                                               527                                                                               463                                                                               483                                                                               465                                                                               459                                                                               443                           Adhesion, pli                                                                               182  174    251                                                                               220                                                                               245                                                                               225                                                                               236                                                                               230                                                                               196                                                                               216                                                                               228                           __________________________________________________________________________

All of the compositions except the comparative example, which contains only urea, exhibit improved adhesion over Control B.

EXAMPLES 13-21

Glyoxal (40% aqueous solution containing 0.4% formaldehyde) and the urea-glyoxal reaction products of Examples L-S above, obtained therefrom are absorbed onto precipitated, hydrous calcium silicate and incorporated into natural rubber as a free-flowing solid.

    __________________________________________________________________________     % Active*       Control C                                                                            13                                                                               14                                                                               15                                                                               16                                                                               17                                                                               18                                                                               19                                                                               20                                                                               21                                       __________________________________________________________________________     Compositions                                                                   Natural rubber masterbatch                                                                     158.5                                                          Sulfur          3.75                                                           N-oxydiethylene benzo-                                                                         0.8                                                            thiazole-2-sulfenamide                                                         Glyoxal               3                                                        Urea-Glyoxal Reaction Products                                                 0.5/1   50              3                                                      1.0/1   57.5              3                                                    1.5/1   62                  3                                                  2.0/1   63.2                  3                                                2.5/1   65.5                    3                                              3.0/1   67.9                      3                                            3.5/1   65.3                        3                                          4.0/1   65.6                          3                                        __________________________________________________________________________      *Remainder silicate                                                      

The compositions are compounded and vulcanized as described in Examples 4-12. Results are given below.

    __________________________________________________________________________     Stress-Strain                                                                  and Adhesion Properties                                                                    Control C                                                                            13 14 15 16 17 18 19 20 21                                   __________________________________________________________________________     Modulus @ 300%, psi                                                                        1629  1478                                                                              1516                                                                              1776                                                                              1871                                                                              1935                                                                              2261                                                                              2371                                                                              2308                                                                              2261                                 Tensile, psi                                                                               3868  3288                                                                              3360                                                                              3639                                                                              3449                                                                              3557                                                                              3852                                                                              3767                                                                              3763                                                                              3693                                 Elongation, %                                                                               533   519                                                                               510                                                                               507                                                                               468                                                                               492                                                                               485                                                                               440                                                                               445                                                                               466                                 Adhesion, pli                                                                               172   194                                                                               222                                                                               216                                                                               223                                                                               243                                                                               230                                                                               222                                                                               215                                                                               216                                 __________________________________________________________________________

EXAMPLES 22-23

Following the procedure of Examples 13-21, reaction products of urea and glyoxal, prepared at high ratios of urea to glyoxal (Examples T&U) are absorbed onto precipitated, hydrous calcium silicate and evaluated in natural rubber.

    __________________________________________________________________________                           % Active*                                                                            Control D                                                                            22   23                                      __________________________________________________________________________     Composition                                                                    Natural rubber masterbatch  158.5                                              Sulfur                      3.75                                               N-oxydiethylene benzothiazole-2-sulfenamide                                                                0.8                                                Urea-Glyoxal Reaction Product                                                   6/1                  60          3                                            10/1                  60               3                                       Stress-Strain and Adhesion Properties                                          Modulus @ 300%, psi         1776  2222 2215                                    Tensile, psi                4117  3719 3646                                    Elongation, %               548   461  450                                     Adhesion, pli               185   223  208                                     __________________________________________________________________________      *remainder silicate                                                      

EXAMPLES 24-28

Following the procedure of Examples 13-21, glyoxal on said silicate, and various urea-glyoxal reaction products of Examples M, N, O, and S, absorbed on said silicate, are evaluated in a blend of natural and synthetic rubber.

    __________________________________________________________________________                           % Active*                                                                            Control E                                                                            24   25   26   27   28                       __________________________________________________________________________     Compositions                                                                   Polyblend masterbatch       159                                                Sulfur                      2.4                                                N-oxydiethylene benzothiazole-2-sulfenamide                                                                1.25                                               Glyoxal               49.8        3                                            Urea-Glyoxal Products                                                          1.0/1  57.5                            3                                       1.5/1  62                                   3                                  2.0/1  63.2                                      3                             4.0/1  65.6                                           3                        Stress-Strain and Adhesion Properties                                          Modulus @ 300%, psi         1932  1695 1668 1767 1805 1974                     Tensile, psi                3204  2998 3083 2809 2595 2865                     Elongation, %               423   463  459  415  386  396                      Adhesion, pli               117   177  193  188  197  164                      __________________________________________________________________________      *remainder silicate                                                      

EXAMPLES 29-31

1-Methylol-4,5-dihydroxy-2-imidazolidinone (MMDHEU; Example V) and 1,3-dimethylol-4,5-dihydroxy-2-imidazolidinone (DMDHEU; Example W) and dihydroxyethyleneurea (DHEU; Example A) are evaluated in a blend of natural and synthetic rubber following the procedure of Examples 24-28.

    __________________________________________________________________________                           Control F                                                                            29   30   31                                       __________________________________________________________________________     Compositions                                                                   Polyblend masterbatch 159                                                      Sulfur                2.4                                                      N-oxydiethylene benzothiazole-2-sulfenamide                                                          1.25                                                     DHEU                        3                                                  MMDHEU                           3.75                                          DMDHEU                                3.5                                      Stress-Strain and Adhesion Properties                                          Modulus @ 300%, psi   1932  1921 1651 1665                                     Tensile, psi          3204  3089 3196 3079                                     Elongation, %         423   416  463  452                                      Adhesion, pli         117   223  204  201                                      __________________________________________________________________________

EXAMPLE 32

Following the procedure of Examples 1-4, dihydroxyethylene urea is evaluated as an adhesion promoter in natural rubber stock. No silica is used in the natural rubber master-batch.

    ______________________________________                                                            Control G                                                                               32                                                 ______________________________________                                         Natural Rubber Masterbatch                                                                          148.5      148.5                                          Sulfur               3.75       3.75                                           N-oxydiethylene benzothiazole-2-                                                                    0.8        0.8                                            sulfenamide                                                                    Dihydroxyethyleneurea           3.0                                            ______________________________________                                    

The compositions are compounded on a standard rubber mill for 10 minutes at 120°-175° F., embedded with 15 brass-coated steel wires, placed parallel, and vulcanized at 307° F. Properties are given below.

    ______________________________________                                         Stress-Strain and Adhesion Properties                                                                Control G 32                                             ______________________________________                                         Modulus @ 300%, psi   1644      1698                                           Tensile, psi          4250      4131                                           Elongation, %         558       536                                            Adhesion, pli         126       193                                            ______________________________________                                    

The data illustrate that dihydroxyethyleneurea provides improved adhesion in the absence of silica.

EXAMPLES 33-41

When the procedure of Examples 13-21 is again followed except that the Masterbatch is devoid of high surface area silica, results similar to those shown in Example 32 are achieved.

EXAMPLE 42

The procedure of Example 4 is again followed except that the glyoxal solution is replaced by pure anhydrous, monomeric glyoxal and the masterbatch and glyoxal are compounded at a temperature of below 50° C. When the resultant material is tested, similar results are achieved.

EXAMPLE 43

When the glyoxal solution of Example 4 is distilled in vacuo to 5% water and the resultant material is compounded with rubber as set forth therein, excellent results are observed. 

I claim:
 1. A method for forming a strong adhesive bond between a vulcanized natural or synthetic rubber composition and a textile fiber or metal wire embedded therein which comprises embedding a textile fiber or metal reinforcing material in a vulcanizable rubber composition consisting essentially of (A) natural or synthetic rubber, or a mixture thereof; (B) a vulcanizing agent; and (C) from about 1 to 10 parts by weight, per hundred parts by weight of rubber, of (a) glyoxal, (b) a reaction product of glyoxl and from 0.1 to 10 molar proportions of urea or (c) a reaction product of glyoxal, 0.1 to 10 molar proportions of urea and from 0.01 to 2 molar proportions of formaldehyde per molar proportion of glyoxal and vulcanizing said composition.
 2. A method according to claim 1 wherein said rubber is natural rubber, polybutadiene, polyisoprene, ethylenepropylene terpolymer rubber, butadiene-styrene copolymer rubber, butadieneacrylonitrile copolymer rubber, chloroprene rubber, chlorosulfonated polyethylene, or mixtures thereof.
 3. A method according to claim 2 wherein said rubber is natural rubber.
 4. A method according to claim 1 wherein said glyoxal compound contains from 0.01 to 0.4 molar proportions of formaldehyde.
 5. A method according to claim 1 containing from 0.1 to 10 molar proportions of urea and from 0.01 to 0.4 molar proportions of formaldehyde per molar proportion of glyoxal.
 6. A method according to claim 1 containing from 0.5 to 4 molar proportions of urea and from 0.01 to 0.4 molar proportions of formaldehyde per molar proportion of glyoxal.
 7. A method according to claim 1 containing from about 1 to 1.5 molar proportions of urea and from 0.1 to 2 molar proportions of formaldehyde per molar proportion of glyoxal.
 8. A method according to claim 1 wherein said (c) is formaldehyde-free, aqueous glyoxal.
 9. A method according to claim 1 wherein said (c) is the reaction product of formaldehyde-free, aqueous glyoxal, and 0.1-10.0 moles of urea.
 10. A method according to claim 9 wherein the molar ratio of said glyoxal and said urea ranges from about 1:1 to about 1:1.5, respectively.
 11. A method according to claim 7, containing 4,5-dihydroxy-2-imidazolidinone.
 12. A method according to claim 7 containing 1-methylol-4,5-dihydroxy-2-imidazolidinone.
 13. A method according to claim 7 containing 1,3-dimethylol-4,5-dihydroxy-2-imidazolidinone.
 14. A method according to claim 1 wherein said (c) is absorbed on an inert solid carrier.
 15. A method according to claim 14 wherein said carrier is hydrous calcium silicate.
 16. A method according to claim 1 wherein said composition additionally comprises (D) from about 2 to 14 parts by weight, per hundred parts by weight of rubber, of a high surface area silica.
 17. A method according to claim 16 wherein said silica comprises 8 to 12 parts per hundred of rubber.
 18. A method according to claim 1 wherein said rubber composition additionally comprises (E) carbon black.
 19. A vulcanized rubber reinforced with a textile fiber or steel wire obtained by the method of claim
 1. 